CN115584228A - Quartz special material and preparation method thereof - Google Patents
Quartz special material and preparation method thereof Download PDFInfo
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- CN115584228A CN115584228A CN202211094262.XA CN202211094262A CN115584228A CN 115584228 A CN115584228 A CN 115584228A CN 202211094262 A CN202211094262 A CN 202211094262A CN 115584228 A CN115584228 A CN 115584228A
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- pvc
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- alkali
- glass fiber
- epoxy resin
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000010453 quartz Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000003365 glass fiber Substances 0.000 claims abstract description 82
- 239000003822 epoxy resin Substances 0.000 claims abstract description 64
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 64
- 239000003513 alkali Substances 0.000 claims abstract description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003292 glue Substances 0.000 claims abstract description 8
- 239000004611 light stabiliser Substances 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 29
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- 238000005530 etching Methods 0.000 claims description 21
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 21
- 229920006295 polythiol Polymers 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 10
- 239000005770 Eugenol Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 10
- 229960002217 eugenol Drugs 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- -1 benzoic peroxide Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 10
- 229920000915 polyvinyl chloride Polymers 0.000 description 90
- 239000004800 polyvinyl chloride Substances 0.000 description 90
- 230000000052 comparative effect Effects 0.000 description 29
- 229920006335 epoxy glue Polymers 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
The application relates to the technical field of special glass, in particular to a quartz special material and a preparation method thereof. A quartz special material is prepared from the following raw materials in percentage by weight: 30-40% of alkali-etched glass fiber, 10-25% of modified PVC, 30-40% of epoxy resin glue, 1-5% of benzene, 1-3% of lubricant, 1-5% of ferrite yellow and 1-5% of light stabilizer. The quartz special material has excellent alkali resistance, and the components in the quartz special material have excellent bonding force.
Description
Technical Field
The application relates to the technical field of special glass, in particular to a quartz special material and a preparation method thereof.
Background
Quartz glass is special industrial technical glass which is prepared by taking crystal, silica and silicide as raw materials and carrying out high-temperature melting or chemical vapor deposition. The quartz glass has high temperature resistance, low expansion coefficient, good thermal shock resistance and electrical insulation performance, can transmit ultraviolet rays and infrared rays, and has better acid resistance to common acids except hydrofluoric acid and hot phosphoric acid.
However, since the main component of the silica glass is silica, which is an acidic oxide, when the silica glass is exposed to an alkaline environment for a long time, the silica glass is inevitably and gradually etched by the alkali, and thus, there is a need for a special silica glass having excellent alkali resistance.
Disclosure of Invention
In order to improve the alkali resistance of quartz glass, the application provides a quartz special material and a preparation method thereof.
In a first aspect, the present application provides a quartz special material, which adopts the following technical scheme:
a quartz special material is prepared from the following raw materials in percentage by weight: 30-40% of alkali-etched glass fiber, 10-25% of modified PVC, 30-40% of epoxy resin adhesive, 1-5% of benzene, 1-3% of lubricant, 1-5% of iron yellow and 1-5% of light stabilizer.
PVC, namely polyvinyl chloride, has extremely excellent strength, rigidity, hardness and acid and alkali resistance, so when the PVC is prepared by blending the PVC and glass fibers, the PVC can effectively improve the alkali resistance of glass.
However, the special quartz material prepared by blending PVC and glass has poor tensile strength because the compatibility and adhesion of PVC and glass are poor. In contrast, the applicant firstly thinks that the glass fiber is subjected to alkali etching, so that the surface of the glass fiber is subjected to rough treatment, and then the interaction force between the PVC and the alkali-etched glass fiber is increased, and the tensile strength of the quartz special material is indirectly improved.
In addition, due to the blending preparation of the PVC and the alkali-etched glass fiber, the PVC can cover the alkali-etched point limited by the alkali-etched glass and can also protect the whole alkali-etched glass fiber, so that the final alkali resistance of the quartz special material cannot be influenced by the alkali-etched operation.
However, the alkali etching operation on the glass fiber can only limit the PVC in terms of physical effect, and after the quartz special glass is used for a long time, the PVC or alkali etched glass fiber is likely to be worn, so that the interaction force between the PVC and the alkali etched glass fiber is obviously weakened.
Therefore, the applicant thinks that the epoxy resin has excellent bonding performance to glass and PVC, and the epoxy resin has relatively good acid and alkali resistance, so that after the epoxy resin is additionally added to the PVC and the alkali-etched glass fiber, the epoxy resin can simultaneously bond the alkali-etched glass fiber and the PVC, and further effectively improve the tensile strength of the quartz special material.
The lubricant and benzene are used for reducing the processing difficulty of the quartz special material, the light stabilizer is used for improving the problem of poor light resistance caused by PVC addition, and the iron yellow is used for controlling the color of the quartz special material.
Preferably, the modified PVC is one of amino-functionalized PVC, silane-functionalized PVC, and polythiol-functionalized PVC.
Preferably, the modified PVC is prepared from a compatilizer and PVC through a melt extrusion grafting method, wherein the mass ratio of the compatilizer to the PVC is 1: (5-7), wherein the compatilizer is one of 3-mercaptopropyltriethoxysilane, diamino diphenyl sulfone and polythiol.
By using a melt extrusion grafting method, after organic molecules such as functional amino, silane, mercaptan and the like are grafted on the surface of PVC by using 3-mercaptopropyltriethoxysilane, diaminodiphenyl sulfone and polythiol, the interaction of the PVC and epoxy resin is obviously enhanced, so that the bonding performance of the PVC and the epoxy resin is effectively increased, and the tensile strength of the quartz special material is improved.
Wherein, when the mass ratio of the compatilizer to the PVC is 1: (5-7), especially under the mass ratio of 1. Moreover, compared with silane-functionalized PVC and amino-functionalized PVC, the bonding property of the polythiol-functionalized PVC and the epoxy resin is particularly outstanding, so that the tensile strength of the quartz special material using the polythiol-functionalized PVC is more excellent.
Preferably, the epoxy resin glue is formed by mixing modified epoxy resin and a modified curing agent,
the modified epoxy resin is prepared from the following raw materials in parts by weight: 90-110 parts of eugenol, 200-300 parts of epichlorohydrin, 40-60 parts of liquid caustic soda, 1-3 parts of tetramethylammonium chloride and 20-30 parts of tetramethyldisiloxane.
When the eugenol epoxy resin is prepared, the raw material is additionally added with tetramethyldisiloxane to form a bio-based eugenol epoxy silane coupling agent, and when the coupling agent is used in cooperation with the eugenol epoxy resin, the bonding effect of epoxy resin glue, PVC and alkali-etched glass fibers can be effectively enhanced, so that the quartz special material using the modified epoxy resin has better tensile strength.
Preferably, the preparation method of the modified epoxy resin comprises the following steps:
a1, mixing eugenol and epichlorohydrin, then sequentially adding tetramethyldisiloxane and tetramethylammonium chloride, then carrying out catalytic condensation reaction at the temperature of 100-150 ℃ for 6-9h, then cooling to 50-70 ℃, adding liquid alkali, and finally extracting, washing and drying to obtain a condensation compound;
and A2, dissolving the condensate in dichloromethane, oxidizing the condensate by benzoic peroxide at the temperature of 10-20 ℃ for 48-60h, and finally extracting and drying to obtain the modified epoxy resin.
When the modified epoxy resin is prepared by adopting the parameters, the syringyl epoxy resin and the bio-based eugenol epoxy silane coupling agent can be formed more simply and conveniently, so that the quartz special material introduced with the modified epoxy resin has more excellent tensile strength.
Preferably, the modified curing agent is prepared from the following raw materials in parts by weight: 20-40 parts of diethylenetriamine and 10-30 parts of thiourea.
Diethylenetriamine is a common aliphatic amine polyamine, which can complete addition reaction with other compounds such as organic ketone, epoxy ring and the like, and a system consisting of the product and epoxy resin fat is decomposed into amine to cure the epoxy resin.
The diethylenetriamine has the advantages of low toxicity and good compatibility, but the curing speed is slow, the service life is relatively short, and the bonding effect of the epoxy resin adhesive using the diethylenetriamine to other substances is obviously poor after the diethylenetriamine is stored for a long time. And the thiourea functional group is introduced into the diethylenetriamine molecular structure to form the epoxy resin curing agent containing thiourea polyamine, so that the epoxy resin is promoted to maintain excellent bonding performance for a long time, and the tensile strength of the quartz special material is improved.
Preferably, the preparation method of the modified curing agent comprises the following steps: mixing diethylenetriamine and thiourea, and then reacting for 2-4h at the temperature of 120-150 ℃ to finally obtain the modified curing agent.
Under the reaction temperature and the reaction time, the reaction between the diethylenetriamine and the thiourea can be more stable and effective, and the tensile strength of the quartz special material is indirectly improved.
Preferably, the preparation method of the alkali-etched glass fiber comprises the following steps:
b1, preheating glass fibers, and then flatly paving to form a glass fiber net;
b2, spraying the alkali etching solution onto a glass fiber net in a spraying manner, and then carrying out alkali etching for 2-3 hours at the temperature of 70-80 ℃ to obtain an alkali etching glass fiber crude product;
and B3, soaking the alkali-etched glass fiber crude product in an acidic neutralizing solution, stirring, washing with water, and drying to obtain the alkali-etched glass fiber.
Compared with the method of directly soaking the glass fiber in the alkaline etching solution, the method has the advantages that the alkaline etching points on the surface of the glass fiber can be more uniform by adopting a spraying mode, the possibility of large-area holes on the surface of the glass fiber is effectively reduced, the influence of the alkaline etching on the glass fiber is reduced, and the tensile strength of the quartz special material is indirectly improved.
Preferably, the alkaline etching solution is a water-soluble substance of potassium permanganate and sodium hydroxide, the concentration of the potassium permanganate is 50-70g/L, and the concentration of the sodium hydroxide is 30-50g/L; the acid neutralizing solution is an aqueous solution of sulfuric acid and oxalic acid, the concentration of the oxalic acid is 25-35g/L, and the concentration of the sulfuric acid is 180-200g/L.
The oxalic acid can react with potassium permanganate, thereby eliminating the potassium permanganate and effectively reducing the influence of the potassium permanganate on the glass fiber.
In a second aspect, the application provides a preparation method of a quartz special material, which adopts the following technical scheme: a preparation method of quartz special material comprises the following steps:
s1, mixing epoxy resin glue, benzene, a lubricant and a light stabilizer, sequentially adding alkali etched glass fiber, modified PVC and iron yellow, and uniformly stirring to obtain a quartz special material mixture;
s2, heating the quartz special material mixture to 140-160 ℃, then carrying out extrusion forming, and finally cooling to obtain the quartz special material.
In summary, the present application has the following beneficial effects:
1. performing alkali etching on the glass fiber, so as to perform rough treatment on the surface of the glass fiber, further increase the interaction force between PVC and the alkali-etched glass fiber, and indirectly improve the tensile strength of the quartz special glass;
2. after the epoxy resin is additionally added into the PVC and the alkali-etched glass fiber, the epoxy resin can simultaneously bond the alkali-etched glass fiber and the PVC, so that the tensile strength of the quartz special material is effectively improved;
3. benzene can be used as a solvent of the hard PVC and the epoxy resin, so that the bonding performance of the hard PVC and the epoxy resin is effectively improved.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
Raw materials
Medium alkali glass fiber boulder 988JSWX016; PVC CAS:9002-86-2; zinc stearate CAS:557-05-1; bis (2, 6-tetramethylpiperidinyl) sebacate CAS:52829-07-9; iron yellow CAS:64294-91-3; 3-mercaptopropyltriethoxysilane CAS:14814-09-6; diamino diphenyl sulfone CAS:4273-98-7; polythiol CAS:7575-23-7; eugenol CAS:97-53-0; epichlorohydrin CAS:106-89-8; liquid alkali 32wt% CAS:1310-73-2; tetramethylammonium chloride CAS:75-57-0; tetramethyldisiloxane CAS:3277-26-7; dichloromethane CAS:75-09-2; benzoic acid peroxide CAS:93-59-4; diethylenetriamine CAS:111-40-0; thiourea CAS:62-56-6; CAS of potassium permanganate: 7722-64-7; sodium hydroxide CAS:1310-73-2; sulfuric acid 98%: 7664-93-9; oxalic acid CAS:144-62-7.
Examples
Example 1
The preparation method of the quartz special material comprises the following steps:
s1, mixing 35wt% of epoxy resin adhesive, 2wt% of benzene, 2wt% of lubricant-zinc stearate and 2wt% of light stabilizer-bis (2, 6-tetramethyl piperidyl) sebacate, then sequentially adding 36wt% of alkali etched glass fiber, 21wt% of modified PVC and 2wt% of ferrite yellow, and then uniformly stirring to obtain a quartz special material mixture;
s2, heating the quartz special material mixture to 150 ℃ (140-160 ℃), then carrying out extrusion forming under the pressure of 100Mpa, and finally cooling to obtain the quartz special material;
wherein the epoxy resin glue is formed by mixing modified epoxy resin and a modified curing agent in a weight ratio of 5;
the preparation method of the modified epoxy resin comprises the following steps:
a1, mixing 100kg of eugenol and 250kg of epoxy chloropropane at a stirring speed of 500r/min for 10min, then sequentially adding 2kg of tetramethyl disiloxane and 25kg of tetramethyl ammonium chloride, then carrying out catalytic condensation reaction at a temperature of 130 ℃ for 8h, then cooling to 60 ℃, adding 50kg of liquid alkali, and finally extracting, washing and drying to obtain a condensation compound;
a2, dissolving the condensate in 500kg of dichloromethane, oxidizing the condensate by 10kg of benzoic peroxide at 15 ℃ for 54h, and finally extracting and drying to obtain modified epoxy resin;
the preparation method of the modified curing agent comprises the following steps: mixing 30kg of diethylenetriamine and 15kg of thiourea at a stirring speed of 500r/min for 20min, and then reacting at the temperature of 140 ℃ for 3h to finally obtain a modified curing agent;
the preparation method of the modified PVC comprises the following steps: adding 3-mercaptopropyltriethoxysilane and PVC into a screw extruder according to the mass ratio of 1;
the preparation method of the alkali-etched glass fiber comprises the following steps:
b1, preheating glass fibers at the temperature of 200 ℃ for 2 hours, and then flatly paving the glass fibers to form a glass fiber net;
b2, spraying the alkali etching solution onto a glass fiber net in a spraying manner, and then carrying out alkali etching for 2.5 hours (preferably 2-3 hours) at 75 ℃ (preferably 70-80 ℃) to obtain an alkali-etched glass fiber crude product;
b3, soaking the alkali-etched glass fiber crude product in an acidic neutralizing solution, stirring for 2 hours at a stirring speed of 200r/min, washing with water, and drying to obtain alkali-etched glass fiber;
wherein the alkaline etching solution is water soluble potassium permanganate and sodium hydroxide, the concentration of potassium permanganate is 60g/L (preferably 50-70 g/L), and the concentration of sodium hydroxide is 40g/L (preferably 30-50 g/L); the acidic neutralizing solution is an aqueous solution of sulfuric acid and oxalic acid, the concentration of the oxalic acid is 30g/L (25-35 g/L is suitable), and the concentration of the sulfuric acid is 190g/L (180-200 g/L is suitable).
Examples 2 to 5
The difference from example 1 is that the weight percentages of the components in the quartz special material are different, as shown in table 1.
TABLE 1 weight percent table of quartz specialty materials for examples 1-5
Example 6
The difference from example 1 is that the silane functionalized PVC is replaced with the same weight percentage of amino functionalized PVC; amino-functionalized PVC differs from silane-functionalized PVC only in that 3-mercaptopropyltriethoxysilane is replaced by diaminodiphenylsulfone in the preparation process.
Example 7
The difference from example 1 is that the silane-functionalized PVC was replaced with the same weight percentage of polythiol-functionalized PVC;
polythiol-functionalized PVC differs from silane-functionalized PVC only in that 3-mercaptopropyltriethoxysilane is replaced by a polythiol in the preparation process.
Example 8
The difference from example 7 is that the mass ratio of polythiol to PVC is 1:5.
example 9
The difference from example 7 is that the mass ratio of polythiol to PVC is 1:7.
example 10
The difference from example 7 is that the mass ratio of polythiol to PVC is 1:4.
example 11
The difference from example 7 is that the mass ratio of polythiol to PVC is 1:8.
example 12
The difference from example 7 is that the weight of each component of the modified epoxy resin in the epoxy resin adhesive is different, as shown in table 2.
TABLE 2 weight table (kg) of modified epoxy resin compositions in example 7 and examples 12 to 15
Examples 16 to 19
The difference from example 7 was that the amount of tetramethyldisiloxane added was varied, as shown in Table 3.
TABLE 3 addition amount of tetramethyldisiloxane (kg) in examples 7 and 16 to 19
| Example 7 | Example 16 | Example 17 | Example 18 | Example 19 | |
| Tetramethyldisiloxane | 25 | 30 | 20 | 15 | 35 |
Example 20
The difference from example 7 is that no tetramethyldisiloxane is added to the epoxy resin glue.
Example 21
The difference from example 7 is that in the preparation method of the modified epoxy resin, the catalysis temperature is 100 ℃, the catalysis time is 6h, the cooling temperature is 50 ℃, the oxidation temperature is 10 ℃, and the oxidation time is 48h.
Example 22
The difference from example 7 is that in the preparation method of the modified epoxy resin, the catalysis temperature is 150 ℃, the catalysis time is 9h, the cooling temperature is 70 ℃, the oxidation temperature is 20 ℃, and the oxidation time is 60h.
Examples 23 to 26
The difference from example 7 is that the epoxy resin adhesive has different weight of each component of the modified curing agent, as shown in table 4.
TABLE 4 weight table (kg) of modified curing agent components in example 7 and examples 23 to 26
| Example 7 | Example 23 | Example 24 | Example 25 | Example 26 | |
| Diethylenetriamine | 30 | 40 | 20 | 10 | 50 |
| Thiourea | 20 | 10 | 30 | 40 | 0 |
Example 27
The difference from example 7 is that the reaction temperature in the modified curing agent preparation method was 120 ℃ and the reaction time was 2 hours.
Example 28
The difference from example 7 is that the reaction temperature in the modified curing agent preparation method was 150 ℃ and the reaction time was 4 hours.
Example 29
The difference from example 7 is that in the method for producing alkali-etched glass fibers, no preheating operation is performed in B1.
Example 30
The difference from example 7 is that in the method for producing alkali-etched glass fibers, the glass fiber web is directly immersed in the alkali-etching solution in B2.
Example 31
The difference from example 7 is that oxalic acid was not added to the neutralization solution.
Comparative example
Comparative example 1
A quartz special material is extruded by glass fiber only.
Comparative example 2
The difference from example 1 is that the alkali etched glass fibers were replaced with glass fibers, the silane functionalized PVC was replaced with PVC, and no epoxy glue was added.
Comparative example 3
The difference from example 1 is that the silane-functionalized PVC is replaced with PVC without the addition of epoxy glue.
Comparative example 4
The difference from example 1 is that the silane-functionalized PVC is replaced with PVC.
Performance test
Detection method
1. Alkali resistance test
From example 1 and comparative examples 1 to 4, 3 samples (10. + -. 0.80g of each sample) were taken, and each sample was weighed and recorded to obtain M 0 . All samples were then soaked in liquid caustic (30 wt%) for 2h, then removed and transferred to a sulfuric acid solution (50 wt%) for 2h, finally washed and dried, then weighed again and recorded to give M.
Then according to (M) 0 -M) 100% formula to obtain the amount of alkaline etching loss of each sample, and finally taking the same realThe average data of the samples of the examples or comparative examples are shown in Table 5 as the values of the alkali resistance properties thereof.
TABLE 5 alkali-resistant Properties of example 1 and comparative examples 1 to 4 Table (g)
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Amount of loss | 0.05 | 1.33 | 0.11 | 0.11 | 0.06 |
2. Adhesion Performance test
Three samples were taken from examples 1 to 31 and comparative examples 2 to 4, respectively, and then the tensile strength of the samples was measured with reference to GB/T1040.1-2006 "determination of tensile Properties of plastics", and finally the tensile strength was obtained and averaged.
TABLE 6 adhesion Properties tables (MPa) of examples 1 to 31 and comparative examples 1 to 4
| Tensile strength | Tensile strength | ||
| Example 1 | 32.3 | Example 18 | 33.3 |
| Example 2 | 32.1 | Example 19 | 33.1 |
| Example 3 | 31.3 | Example 20 | 32.7 |
| Example 4 | 31.1 | Example 21 | 34.8 |
| Example 5 | 30.6 | Example 22 | 35.2 |
| Example 6 | 33.7 | Example 23 | 34.7 |
| Example 7 | 35.2 | Example 24 | 33.1 |
| Example 8 | 35.2 | Example 25 | 30.2 |
| Example 9 | 34.3 | Example 26 | 32.1 |
| Example 10 | 35.3 | Example 27 | 34.7 |
| Example 11 | 33.9 | Example 28 | 35.3 |
| Example 12 | 34.8 | Example 29 | 34.8 |
| Example 13 | 34.6 | Example 30 | 34.9 |
| Example 14 | 34.3 | Example 31 | 34.7 |
| Example 15 | 34.5 | Comparative example 2 | 9.1 |
| Example 16 | 34.1 | Comparative example 3 | 10.3 |
| Example 17 | 33.9 | Comparative example 4 | 30.1 |
As can be seen by combining example 1 and comparative examples 1 to 4 with table 5, the loss amount of comparative examples 2 to 3 is significantly reduced compared to comparative example 1, thereby demonstrating that PVC can effectively protect glass fibers, thereby effectively reducing the loss amount of glass fibers in a strong alkaline environment.
Compared with comparative examples 2-3, the loss of the embodiment 1 and the comparative example 4 is further reduced because the bonding performance between PVC and the glass fiber is relatively poor, so a certain gap exists between the glass fiber and the PVC, and the epoxy resin can supplement the gap, thereby effectively reducing the possibility that liquid alkali enters the gap, and further reducing the loss of the quartz special material in the strong alkali liquid.
It can be seen from the combination of example 1, comparative examples 2-4 and table 6 that the tensile strength of comparative example 3 is slightly improved compared to comparative example 2, which shows that the use of alkali-etched glass fiber can promote the quartz special material to have better tensile strength compared to the use of glass fiber, and the reason for this is that alkali-etched holes exist on the surface of alkali-etched glass fiber, so that PVC can physically limit the alkali-etched glass fiber through the alkali-etched holes.
The tensile strength of comparative example 4 is significantly improved compared to comparative example 3, because the adhesion between PVC and glass fiber is relatively poor, and the epoxy resin can stably adhere PVC and glass fiber.
The reason why the tensile strength of example 1 is further improved compared to comparative example 4 is that the adhesion between PVC and epoxy resin is relatively poor, and PVC can be more stably adhered to epoxy resin after functional groups are grafted on the surface of PVC.
In combination with examples 1 to 5 and Table 6, it can be seen that the tensile strengths of examples 2 to 3 are slightly reduced and the tensile strengths of examples 4 to 5 are further reduced compared to example 1, thereby showing that the components of the quartz specialty material can be more stably bonded in the range of examples 1 to 3, particularly in the range of example 1.
Combining example 1, examples 6-7, and table 6, it can be seen that the tensile strength of example 6 is slightly increased relative to example 1, while the tensile strength of example 7 is significantly increased, thus demonstrating that the adhesion of polythiol-functionalized PVC to epoxy resin is particularly outstanding relative to silane-functionalized PVC as well as amino-functionalized PVC.
In combination with examples 7-11 and Table 6, it can be seen that the tensile strengths of examples 9 and 11 are gradually decreased, while the tensile strengths of examples 8 and 10 are substantially unchanged, relative to example 7, thus indicating that the bonding performance of the polythiol-functionalized PVC to the epoxy resin is gradually improved as the ratio of the polythiol is increased in the polythiol-functionalized PVC.
However, when the weight ratio of the polythiol to the PVC reaches 1. Also, the cost of the polythiol is relatively high compared to PVC, and therefore, the ratio of example 7 is considered superior.
By combining example 7, examples 12-15 and Table 6, it can be seen that the tensile strengths of examples 12-13 are slightly reduced and the tensile strengths of examples 14-15 are further reduced relative to example 7, thus indicating that the epoxy glue has better adhesion to polythiol-functionalized PVC and glass fibers at the ratio ranges of examples 7 and 12-13, especially at the ratio range of example 7.
In combination with example 7, examples 16-20 and Table 6, it can be seen that the tensile properties of example 20 are significantly reduced compared to example 7, thereby indicating that the addition of tetramethyldisiloxane to the modified epoxy resin can effectively improve the adhesion of the epoxy resin adhesive to polythiol-functionalized PVC and glass fiber.
On the other hand, the tensile strengths of examples 16-17 were significantly reduced and the tensile strengths of examples 18-19 were further reduced compared to example 7, which shows that the epoxy resin adhesive has better adhesion to polythiol-functionalized PVC and glass fibers at the addition ratios of examples 7 and 16-17, especially at the addition ratio of example 7.
Combining example 7, examples 21-22 and table 6, it can be seen that the tensile strength of example 21 is significantly reduced relative to example 7, while the tensile strength of example 22 is essentially unchanged, thus demonstrating that epoxy glue can be made with superior adhesion to polythiol-functionalized PVC and glass fibers if the modified epoxy resin is prepared under the parameters of examples 7 and 22. Among them, the preparation time of example 22 was relatively long compared to example 7, and thus example 7 was still superior.
By combining example 7, examples 23-26 and Table 6, it can be seen that the tensile strength of example 26 is significantly reduced compared to example 7, thus indicating that the epoxy resin adhesive prepared has better adhesion performance to polythiol functionalized PVC and glass fiber when thiourea is added to diethylenetriamine.
On the other hand, the tensile strength of examples 23-24 is slightly reduced and the tensile strength of example 25 is significantly reduced compared to example 7, which shows that the epoxy resin adhesive prepared by the formulation of diethylenetriamine and thiourea in the ranges of example 7 and examples 23-24, especially the proportion of example 7 has more excellent adhesion performance to polymercaptan functionalized PVC and glass fiber.
Combining example 7, examples 27-28 and table 6, it can be seen that the tensile strength of example 27 is significantly reduced relative to example 7, while the tensile strength of example 28 is essentially unchanged, thus demonstrating that epoxy glue can be made more adhesive to polythiol functionalized PVC and glass fibers if the modified curing agent is prepared under the parameters of example 7 and example 27. Among these, the preparation time of example 28 is relatively long compared to example 7, and thus example 7 is still superior.
The combination of example 7 and examples 29-31 with Table 6 shows that the tensile strength of example 29 is slightly reduced compared to example 7 because the absence of the preheating operation increases the formation of alkali-etched holes and thus slightly reduces the adhesion between the polythiol functional PVC, alkali-etched glass fibers and epoxy glue.
The tensile strength of example 30 was also slightly reduced compared to example 7, but the reason for this was that direct immersion in an alkaline etching solution resulted in extensive abrasion of the glass fiber surface, and instead, reduced contact area between the polythiol functional PVC, alkaline etched glass fiber and epoxy glue, and reduced adhesion between the polythiol functional PVC, alkaline etched glass fiber and epoxy glue.
The reason why the tensile strength of example 31 is slightly decreased compared to example 7 is that the absence of oxalic acid is likely to cause residual potassium permanganate on the surface of the alkali-etched glass fiber, and further the alkali-etched glass fiber undergoes a large degree of alkali etching after being stored for a period of time, so that the contact area between the polythiol functional PVC, the alkali-etched glass fiber and the epoxy resin adhesive is reduced, and the adhesion performance between the polythiol functional PVC, the alkali-etched glass fiber and the epoxy resin adhesive is further reduced.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The quartz special material is characterized by being prepared from the following raw materials in percentage by weight: 30-40% of alkali-etched glass fiber, 10-25% of modified PVC, 30-40% of epoxy resin glue, 1-5% of benzene, 1-3% of lubricant, 1-5% of ferrite yellow and 1-5% of light stabilizer.
2. The quartz specialty material of claim 1, wherein: the modified PVC is one of amino functionalized PVC, silane functionalized PVC and polythiol functionalized PVC.
3. The quartz specialty material according to claim 2, wherein the modified PVC is prepared from a compatibilizer and PVC by a melt extrusion grafting method, and the mass ratio of the compatibilizer to the PVC is 1: (5-7), the compatilizer is one of 3-mercaptopropyltriethoxysilane, diamino diphenyl sulfone and polythiol.
4. The quartz specialty material of claim 1, wherein: the epoxy resin adhesive is formed by mixing modified epoxy resin and a modified curing agent,
the modified epoxy resin is prepared from the following raw materials in parts by weight: 90-110 parts of eugenol, 200-300 parts of epichlorohydrin, 40-60 parts of liquid caustic soda, 1-3 parts of tetramethylammonium chloride and 20-30 parts of tetramethyldisiloxane.
5. The quartz specialty material of claim 4, wherein the modified epoxy resin is prepared by a method comprising the steps of:
a1, mixing eugenol and epichlorohydrin, then sequentially adding tetramethyldisiloxane and tetramethylammonium chloride, then carrying out catalytic condensation reaction at the temperature of 100-150 ℃ for 6-9h, then cooling to 50-70 ℃, adding liquid alkali, and finally extracting, washing and drying to obtain a condensation compound;
and A2, dissolving the condensate into dichloromethane, oxidizing the condensate by using benzoic peroxide at the temperature of 10-20 ℃ for 48-60h, and finally extracting and drying to obtain the modified epoxy resin.
6. The quartz special material as claimed in claim 4, wherein the modified curing agent is prepared from the following raw materials in parts by weight: 20-40 parts of diethylenetriamine and 10-30 parts of thiourea.
7. The quartz specialty material of claim 6, wherein the modified curing agent is prepared by: mixing diethylenetriamine and thiourea, and then reacting for 2-4h at the temperature of 120-150 ℃ to finally obtain the modified curing agent.
8. The quartz specialty material of claim 1, wherein said alkali etched glass fiber is prepared by a method comprising the steps of:
b1, preheating glass fibers, and then flatly paving to form a glass fiber net;
b2, spraying the alkali etching solution onto the glass fiber net in a spraying manner, and then performing alkali etching for 2-3 hours at the temperature of 70-80 ℃ to obtain an alkali etching glass fiber crude product;
and B3, soaking the crude alkali-etched glass fiber in an acidic neutralizing solution, stirring, washing with water, and drying to obtain the alkali-etched glass fiber.
9. The quartz specialty material of claim 8, wherein: the alkaline etching solution is a water-soluble substance of potassium permanganate and sodium hydroxide, the concentration of the potassium permanganate is 50-70g/L, and the concentration of the sodium hydroxide is 30-50g/L; the acid neutralizing solution is an aqueous solution of sulfuric acid and oxalic acid, the concentration of the oxalic acid is 25-35g/L, and the concentration of the sulfuric acid is 180-200g/L.
10. A method for producing a quartz specialty material according to any of claims 1-9, comprising the steps of:
s1, mixing epoxy resin glue, benzene, a lubricant and a light stabilizer, sequentially adding alkali-etched glass fiber, modified PVC and iron yellow, and uniformly stirring to obtain a quartz special material mixture;
s2, heating the quartz special material mixture to 140-160 ℃, then carrying out extrusion forming, and finally cooling to obtain the quartz special material.
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